EP4069789B1 - Composition de revêtement à faible teneur en solvant - Google Patents

Composition de revêtement à faible teneur en solvant Download PDF

Info

Publication number
EP4069789B1
EP4069789B1 EP20816206.5A EP20816206A EP4069789B1 EP 4069789 B1 EP4069789 B1 EP 4069789B1 EP 20816206 A EP20816206 A EP 20816206A EP 4069789 B1 EP4069789 B1 EP 4069789B1
Authority
EP
European Patent Office
Prior art keywords
coating composition
epoxy
coating
composition according
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20816206.5A
Other languages
German (de)
English (en)
Other versions
EP4069789A1 (fr
Inventor
Mihyang Kim
SeongWoon MIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel Coatings International BV
Original Assignee
Akzo Nobel Coatings International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Coatings International BV filed Critical Akzo Nobel Coatings International BV
Publication of EP4069789A1 publication Critical patent/EP4069789A1/fr
Application granted granted Critical
Publication of EP4069789B1 publication Critical patent/EP4069789B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/326—Magnesium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate

Definitions

  • This invention relates to a low solvent or solvent-free epoxy coating composition that can be applied by conventional airless spray equipment to provide a fast curing anti-corrosive layer on a substrate.
  • the invention also relates to a method for coating a substrate using such a coating composition.
  • Primers are often used to coat structures, including those that are used or located in marine environments.
  • the primer helps impart good weathering and corrosion resistance, while maintaining good adhesion to the substrate surface and to subsequently applied coatings and finishes.
  • An example of an anticorrosive primer coating composition is described in US2012/0025142 .
  • a problem with a number of primer compositions is that they comprise significant quantities of organic solvents.
  • VOCs volatile organic compounds
  • the present invention relates to a coating composition
  • a coating composition comprising
  • the solids content of the composition is at least 90 wt% and/or the solids volume is at least 90.0 %, when determined according to ASTM D5201-05a.
  • the invention also relates to a method of coating a substrate using such a composition.
  • the coating composition is of particular benefit in corrosion protection and can function as an anticorrosive coating composition.
  • Anticorrosive coating compositions are often alternatively referred to as anticorrosion coatings, corrosion resistant coatings, or corrosion protection coatings.
  • a particular advantage of the coating compositions is the ability to maintain high adhesion to the substrate even after being immersed for extended periods of time.
  • a problem associated with many coatings is that, after immersion, the substrate surface can still suffer some corrosion, for example where there has been some water penetration between the coating and the substrate, which can result in lifting of the coating through loss of adhesion.
  • the compositions described here are able to resist this loss of adhesion, and also inhibit transgression of water across the coating film, which helps improve corrosion resistance of underlying metallic substrates.
  • the substrate is a metal substrate, for example steel.
  • the substrate is part of a structure which is exposed to the elements, such as wind, rain, ice or snow.
  • the structure can be exposed to sea-water, fresh-water or brackish water environments, for example in an off-shore platform, a wind turbine, a ship or other water-borne vehicle.
  • the coating composition is particularly suited to substrates that are submerged for extended periods of time, i.e. ship hulls, ship ballast tanks or sub-surface metallic portions of fixed or floating platforms or shoreside structures.
  • the substrate surface to which the coating is applied does not necessarily have to be on the external surface of the structure.
  • the substrate can be the inside surface of a ballast tank or storage tank, such as a potable water tank.
  • the coating composition forms an epoxy layer on the substrate.
  • the layer can optionally be overcoated, for example to give improved UV radiation or antifouling protection, or to improve colour stability.
  • the coating composition can be coated on a pre-treated substrate, for example on top of a previously applied coating layer.
  • the coating composition is a primer composition, on which other coating layers are optionally added.
  • the coating composition is a universal primer composition.
  • the composition is suitable for being applied onto a surface, e.g. using brush or roller, or using suitable spray equipment. In embodiments, it is suitable for being sprayed by airless spray equipment.
  • the composition can be applied as a single coat, although if desired multiple coats can be applied.
  • the coating composition comprises, inter alia, a binder and a curing agent. These are typically kept separate before use, to avoid premature curing of the binder, i.e. they can be supplied as a so-called 2-K (2 component) composition. Therefore, in embodiments, the coating composition comprises two separate parts, i.e. a first part (A) comprising the binder, and a second part (B) comprising the curing agent. When used, the two parts (A) and (B) are mixed together to form the coating composition and applied to a substrate. The composition then cures to form a layer on the substrate.
  • a binder and a curing agent typically kept separate before use, to avoid premature curing of the binder, i.e. they can be supplied as a so-called 2-K (2 component) composition. Therefore, in embodiments, the coating composition comprises two separate parts, i.e. a first part (A) comprising the binder, and a second part (B) comprising the curing agent. When used, the two parts (A
  • the mixing ratio of the first and second parts of the composition is at least in part determined by the respective amounts of epoxy and active hydrogens present in the total composition.
  • the mixing ratio in solids volume (defined below) of part (A) to part (B) is in the range of from 1:1 to 10:1, such as from 5:1 to 2:1.
  • the coating composition of the invention has a high solids content of at least 90 wt%, and also has a low content of volatile organic compounds (VOC).
  • the solids content is at least 95 wt%, for example at least 99 wt%.
  • the solids content is 100 wt%, i.e. the VOC content is zero (i.e. 0 wt% or 0 g/L).
  • the coating composition of the invention also has a high solids volume% ("VS%"), which in embodiments is at least 90%, for example at least 95%, or at least 99%, for example 100%.
  • VS% solids volume%
  • the solids content (in weight or volume terms) and the VOC content are calculated using method ASTM D5201-05a.
  • solids does not actually represent purely solid components. It instead refers to the non-volatile components of the composition that are assumed to remain in and form part of the coating layer once cured. Thus, it is assumed that volatile components evaporate, and the materials that remain are identified as coatings solids. Solvents can be used to adjust the viscosity for application and appearance of the coating, and are not considered coatings solids since they evaporate. However, other liquid materials, such as plasticisers, reactive diluents, etc. that are not volatile and are expected to be retained in the dried film are generally classified as part of the coating solids.
  • the first binder-containing part (A) can have a solids volume of at least 80%, for example at least 90%.
  • the second curing agent-containing part (B) can have a solids volume of at least 80%, for example at least 90%.
  • the composition contains a very low solvent and VOC content.
  • the solvent content is less than 5 wt%, for example less than 2 wt%, or than 1 wt% solvent.
  • the solvent content is 0.5 wt% or less, and in still further embodiments there is no solvent present.
  • the solvent content (and the VOC content) in each part can be (independently) less than 10 wt%, for example less than 5 wt%, less than 2 wt% or less than 1 wt%, such as 0.5 wt% or less.
  • both parts (A) and (B) contain no solvent.
  • the solvent content (and the VOC content) of the coating composition is typically less than 250 g/L, for example less than 100 g/L, or less than 50 g/L. In some embodiments the solvent content is 25 g/L or less, such as 10 g/L or less.
  • volatile organic compound or its abbreviation "VOC”, when used herein, means an organic compound having an initial boiling point less than or equal to 250 °C measured at a standard atmospheric pressure of 101.3 kPa.
  • no solvent or “no VOC”
  • no added solvent or VOC there may be small amounts present in the component materials of the coating composition (e.g. water may be present in small quantities).
  • the total amount of solvent or VOC is less than 1000 ppm, for example less than 500 ppm in the coating composition.
  • solvent When solvent is present, it can be selected from hydrocarbons and oxygen-containing solvents, for example being selected from alkyl aromatic hydrocarbons (such as xylene and toluene), alcohols, ethers, ketones and esters (such as methyl ethyl ketone, methyl isobutyl ketone, methoxypropanol, butyl acetate, benzyl alcohol, octyl phenol, resorcinol, n-butanol, isobutanol and isopropanol).
  • the solvent comprises from 2 to 20 carbon atoms, for example from 3 to 15 carbon atoms.
  • Water can present, although is typically used in low quantities. If present, it is typically at concentrations of 1 wt% or less of the total coating composition, for example 0.5 wt% or less.
  • the coating composition is typically self-curing, i.e. is able to self-cure once the curing agent and epoxy resin components are mixed, without the need for any additional initiation process, e.g. heat. Curing can take place at ambient temperature, for example in the range of from -10 to 50 °C or from 0 to 40 °C. Heat can optionally be applied should the rate of curing need to be accelerated for any reason.
  • the coating can be applied as a coating layer.
  • VOC and solvent content is low, it also is possible to apply a further coating whilst the first layer is "wet". This enables rapid build-up of layers to create a thicker coating in a shorter period of time. It is also possible to wait until the first layer is cured before applying subsequent layers.
  • the coating composition comprises a binder.
  • the binder can comprise one or more curable epoxy resins.
  • the binder comprises at least one liquid epoxy resin.
  • liquid refers to the state of the epoxy resin at 23°C and 1 atm (1.013 bar).
  • Suitable curable epoxy resins include aromatic epoxy resins, typically having two or more aromatic (or heteroaromatic) groups, for example a diphenylalkyl moiety.
  • the epoxy resin comprises two or more epoxy groups or epoxy ether groups such as glycidyl or glycidyl ether groups.
  • Examples of epoxy resin include bisphenol glycidyl ether and diglycidyl ether resins and resorcinol glycidyl ether and diglycidyl ether resins.
  • Suitable epoxy resins are those whose formula can be represented by Formula (1): Ar 1 (X 1 )-M 1 -Ar 2 (X 2 ) (1)
  • X 1 and X 2 are each independently selected from C 1-12 alkyl or alkoxy groups containing an epoxy ring, for example C 3 -C 6 epoxy ring-containing alkoxy groups such as glycidoxy groups. Either or both of X 1 or X 2 group can optionally be substituted with one or more substituents selected from halide and hydroxy. Where a halide is present, it is typically selected from F and Cl. In embodiments, no halogen atoms are present, and in further embodiments, there are no substituents.
  • the carbon chain in the C 1-12 alkyl or alkoxy group can be linear or branched. In embodiments, X 1 and X 2 are the same.
  • Ar 1 and Ar 2 are each independently selected from aromatic and heteroaromatic groups, e.g. groups with a 5 or 6 membered aromatic ring.
  • Heteroatoms in the heteroaromatic group can be selected from one or more O, S and N atoms, for example from 1 to 3 heteroatoms.
  • the aromatic group does not contain a heteroatom.
  • the aromatic or heteroaromatic group can optionally be substituted with one or more substituents selected from C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl, C 1-6 haloalkoxy, halide and hydroxy. Where halogen is present (i.e.
  • halide or on a haloalkyl or haloalkoxy group
  • it is typically selected from F and Cl.
  • no halogen is present.
  • the optional substituent is selected from C 1-2 alkyl.
  • Ar 1 and Ar 2 are the same.
  • M 1 is a linking group selected from -[C(R 1 ) 2 ] a - and -SO 2 -, where a is from 1 to 3, and each R 1 is, independently and on each occurrence, selected from H and C 1-2 alkyl. In embodiments, M is selected from -CH 2 - and -C(Me) 2 -.
  • the epoxy resin can also be represented by Formula (2) or (3): Ar 1 (X 1 )-M 1 -Ar 2 -[M 2 -Ar 1 (X 1 )-M 1 -Ar 2 ] b -X 2 (2) Ar 1 (X 1 )-M 3 -[Ar 1 (X 1 )-M 3 -] b -Ar 1 (X 1 ) (3)
  • X 1 , X 2 , M 1 , Ar 1 and Ar 2 are as defined above.
  • M 2 is hydroxy-substituted C 1-12 dialkoxy group.
  • M 2 comprises the same number of carbon atoms as X 2 .
  • Ar 1 and Ar 2 can be the same. Additionally, or alternatively, X 1 and X 2 can be the same.
  • M 3 is a C 1-12 aliphatic hydrocarbyl group, e.g. selected from C 1-12 linear, branched or cyclic alkyl groups.
  • Examples include C 1-12 alkylene groups e.g. methylene (-CH 2 -), ethylene (-C 2 H 4 -), isopropyl (-CH(Me)CH 2 -), propyl (-CH 2 CH 2 CH 2 -), and C 5-10 cycloalkyl groups such as cyclohexyl (-C 6 H 10 -) and dicyclopentanyl (-C 10 H 18 -).
  • Cyclic groups can optionally comprise one or more C 1-3 alkyl substituents.
  • the aliphatic hydrocarbyl group is typically saturated, although in embodiments it can be unsaturated, for example comprising one or more double bonds.
  • b can be a number in the range of from 0 to 10, for example from 0 to 5 or from 0 to 2.
  • the number does not have be a whole number, representing the average number of units where there is a mixture.
  • the resin is selected from bisphenol (di)glycidyl ether resins and resorcinol (di)glycidyl ether resins, where the bisphenol is bisphenol A, F or S.
  • bisphenol (di)glycidyl ether resins such as bisphenol A or F resins, have epoxy equivalent weights in the range of from 100 to 800 g/eq, for example in the range of from 140 to 550 g/eq.
  • the resins are so-called Novolac resins, based on a moiety formed from reaction between an aromatic alcohol (e.g. phenol or cresol) and an aldehyde such as formaldehyde, which can then be modified with an epoxy group, e.g. a glycidyl ether group.
  • an aromatic alcohol e.g. phenol or cresol
  • an aldehyde such as formaldehyde
  • Examples include phenol Novolac epoxy resins, such as DEN TM 425, DEN TM 431 and DEN TM 438 (ex DOW Chemicals), Epon TM 154, Epon TM 160, Epon TM 161 and Epon TM 162 (ex. Momentive Performance Chemicals), and Epalloy TM 8250 (ex. Emerald Chemical Co.).
  • epoxy compounds can have an epoxy equivalent weight in the range of 100 to 300, for example 150 to 220 or 165 to 185 g/eq.
  • epoxy resins which may be used include epoxy cresol Novolac resins, such as Epon TM 164 and Epon TM 165 (ex. Momentive Performance Chemicals), or bisphenol A epoxy novolac resins, such as the Epon TM SU range of resins.
  • the epoxy resin can be selected from dicyclopentadiene aromatic glycidyl ether resins, e.g. dicyclopentadiene-cresol glycidyl ether resins.
  • the epoxy resin has a (number average, M n ) molecular weight in the range of from 100 to 2000, for example from 200 to 1000, from 250 to 800, or from 350 to 800.
  • the coating composition can comprise more than one epoxy resin, e.g. blends of any of the above epoxy resins may be used in combination with each other.
  • a blend comprising a bisphenol A and a bisphenol F can be used.
  • a blend of a bisphenol A, a bisphenol F and a Novolac resin can be used.
  • the epoxy resin can be liquid or solid. In embodiments, it is a liquid or (in the case of more than one epoxy resin being present) at least one of the epoxy resins is liquid.
  • liquid bisphenol F epoxy resin with liquid bis-phenol A epoxy resin is used.
  • a mixture of solid or semi-solid bisphenol A epoxy resin can be mixed with liquid bisphenol A or bisphenol F.
  • the epoxy resin in order to minimize the solvent content of any coating composition containing the epoxy resin, it is preferred that the epoxy resin has a low solvent content, e.g., below 20 wt%, or below 10 wt%, based on the weight of epoxy resin. In embodiments, the epoxy resin is free of solvent.
  • the amount of curable epoxy resin in the coating composition is in the range of from 10.0 to 40.0 wt%.
  • the coating composition of the invention can contain at least one organic silane compound.
  • Organic silanes can improve drying properties at low temperature, and can also improve the coating's flexibility, substrate adhesion and anti-corrosive performance.
  • the silane can be included in either part (A) or part (B) of the coating composition, typically in the first binder-containing part (A).
  • the silane compound contains an epoxy group.
  • Silanes of the invention are generally of low molecular weight, for example less than 400 g/mol. Examples of suitable silane compounds are those having general Formula (4): (R 2 ) 4-x SiY d (4)
  • R 2 is an organic group that can optionally have one or more substituents ER 3 .
  • the silane can be alternatively be represented by formula (5). [R 2 (ER 3 ) e ] 4-d SiY d (5)
  • d is an integer in the range of from 1 to 3
  • e represents the number of substituents on the R 2 group.
  • e is a whole number in the range of from 0 to 3.
  • R 2 represents an organic group bound directly to the silicon atom of the silane via a SiC bond.
  • Each R 2 group can be independently selected from linear and branched, saturated and unsaturated aliphatic hydrocarbon groups having from 1 to 12 carbon atoms, for example from 1 to 6 carbon atoms.
  • each R 2 is selected from alkyl and alkenyl groups, and in further embodiments each R 2 is an optionally substituted alkyl group.
  • Each R 2 group can also independently be selected from aliphatic or aromatic cyclic groups, e.g. cycloalkyl, cycloalkenyl and aryl groups, typically having from 5 to 12 atoms in the ring system, for example 5 or 6 atoms in the ring system.
  • cyclic groups can comprise one or more heteroatoms in the ring, for example one or more O or N atoms.
  • each R 2 can be the same or different.
  • group R 2 is optionally substituted, it comprises one or more substituents of formula ER 3 , typically from 1 to 3 ER 3 substituents, for example 1 ER 3 substituent.
  • E is an optional linking group, i.e. it can be present or absent. Where E is absent, there is a direct bond between R 2 and R 3 .
  • E can be selected from -O-, -S-, -OC(O)-, -C(O)-, -C(O)-, -C(O)OC(O)-, -NR 4 -, NCO (isocyanate), -N(R 4 )C(O)-, -N(R 4 )C(O)N(R 4 )- and -C(O)N(R 4 )-, where R 4 is H or C 1-6 alkyl.
  • R 3 is selected from C 1-6 alkyl, C 1-6 alkenyl, aryl, heteroaryl, C 1-6 alkylaryl and C 1-6 alkylheteroaryl, in which the aryl or heteroaryl rings have 5 or 6 atoms in the ring.
  • the R 3 group can optionally be substituted with one or more groups selected from hydroxyl, halogen (such as F, Cl or Br), epoxy, -OR 4 and -NR 4 2 where each R 4 is as defined above.
  • halogen such as F, Cl or Br
  • E is present
  • R 3 is not halogen, but it can be hydrogen.
  • R 3 can be halogen, but not hydrogen.
  • R 3 can also be selected from a polyether group of formula ⁇ CR 2 5 f L g ⁇ R 6 , where f is an integer from 2 to 4, g is an integer from 3 to 20, L is -O- or -NR 5 - and each R 5 and R 6 is independently selected from H and C 1-3 alkyl.
  • E can be the same as L, each R 5 can be selected from H and methyl, and R 6 can be selected from H and C 1-3 alkyl.
  • Integer g can be in the range of from 3 to 8.
  • Integer f can be in the range of from 2 to 3.
  • the organic group can be an isocyanurate, based on a trimer of an isocyanate compound.
  • an ER 3 group either is or contains a group selected from hydroxyl, carboxyl, ester, epoxy, (meth)acrylate, amino, amido, isocyanate, isocyanurate and ureido.
  • R 3 is a group comprising from 1 to 8 carbon atoms, (a C 1-8 alkyl group), and additionally includes an ER 3 substituent where E is oxygen and R 3 is selected from optionally substituted C 1-8 -epoxyalkyl and C 1-8 hydroxyalkyl.
  • Examples of silanes include 3-glycidyloxypropyl silanes and 2,3-dihydroxypropoxypropyl silanes.
  • Each Y is selected from halogen or C 1-6 alkoxy. In embodiments, Y is not halogen. In embodiments, each Y is methoxy or ethoxy.
  • organic silane compounds include methyl trimethoxysilane, methyl triethoxy silane, dimethyl dimethoxy silane, trimethyl ethoxy silane, ethyl trimethoxy silane, propyl triethoxy silane, i-butyl triethoxy silane, octyl trimethoxy silane, octyl triethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxy silane, phenyl trimethoxy silane, phenyl dimethyl ethoxy silane, 3-(glycidoxypropyl) trimethoxy silane 3-glycidoxypropyl methyl diethoxy silane, (3-glycidoxypropyl)triethoxy silane, (3-glycidoxypropyl) hexyl trimethoxy silane, beta-(3,4-epoxycyclohexyl)-ethyl trimethoxy silane,
  • the epoxy-containing silanes comprise an epoxy group, for example a glycidyl or glycidoxy group. Examples include those described in WO2017/068015 at page 16, line 20 to page 18, line 5.
  • the silane can be at least partially condensed, for example comprising Si-O-Si bonds.
  • they can be of Formula (6): (R 2 ) h SiY (3-h) -O[-(R 2 ) h SiY (2-h) -O] k -(R 2 ) h SiY (3-h) (6)
  • h is 1 or 2
  • k can be in the range of from 0 to 30, for example from 0 to 10, or from 0 to 4. k does not have to be a whole number, because it may represent an average where there is a mixture.
  • R 2 and Y are as defined above.
  • the silane is capable of reacting with the epoxy binder, e.g. if the silane compound comprises an amine or polyamine organic group, then it can be included in the curing agent-containing part (B) of a 2-component coating composition. In other embodiments, the silane is can be present in the first part (A) of the composition.
  • Silanes are described in US4927749 , and in WO2017/068015 at page 12, line 18 to page 14, line 2. They are also commercially available, for example being sold under the brand names Dynasylan TM D (Evonik), Silquest TM (Momentive) and Geniosil TM (Wacker).
  • the amount of silane in the final coating composition can be in the range of from 1.0 to 15.0 wt.%, for example 1.0 to 10wt% or 1.5 to 8.0 wt%, such as 1.5 to 6.0 wt% on total weight. In embodiments, the content is 2.0 to 6.0 wt%. Increasing the silane content can decrease the viscosity of the composition.
  • the coating composition can comprise a reactive diluent.
  • a reactive diluent is an additive which behaves like a solvent in reducing the viscosity of a composition but does not contribute to its solvent or VOC content, because it possesses reactive groups which allow it either to bind to the coating resins, or to undergo a chemical reaction independent of the main curing reaction. They are typically of lower viscosity than the epoxy resin binder, and do not generally form mechanically robust coatings in the absence of resin.
  • the reactive diluent can be selected from epoxy-containing resins which are aliphatic, or which comprise no more than one aromatic or heteroaromatic group. They can be represented by Formula (7): R 7 (TR 8 ) m (7) m is an integer from 1 to the number of carbon atoms in the R 7 group.
  • R 7 is a C 1-30 aliphatic or C 5-10 aromatic or heteroaromatic group.
  • Aliphatic groups can be linear, branched or cyclic, or can comprise both cyclic and non-cyclic portions.
  • R 7 can also be selected from C 2-30 aliphatic ether or polyether moieties, e.g. of formula R a [OR b ] n OR c .
  • n is an integer in the range of from 1 to 14.
  • R a , R b and R c are all aliphatic groups, which can be the same or different.
  • Heteroaromatic R 7 groups can comprise one or more heteroatoms, typically from 1 to 3 heteroatoms, for example 1 or 2 heteroatoms. They are typically independently selected from O, S and N, for example from O and N.
  • the R 7 group in addition to the TR 8 substituent(s), can optionally be substituted with one or more further substituents selected from halide and hydroxy, for example from 1 to 5 substituents or from 1 to 3 substituents.
  • substituents of aromatic or heteroaromatic groups can additionally include C 1-12 alkyl, C 2-12 alkenyl and C 1-12 alkoxy groups. If halide is present, it is typically selected from F and CI, although in embodiments, there are no halide substituents.
  • R 8 is a reactive group selected from C 2-8 epoxy, C 2-8 olefin, acrylate and C 1-8 alkyl acrylate.
  • R 8 is selected from C 2-8 epoxy and C 2-8 olefin.
  • R 8 groups can optionally comprise one or more further substituents, e.g. from 1 to 5 or from 1 to 3 further substituents, selected from halide, hydroxy, C 1-4 alkoxy and C 1-4 haloalkoxy. If halide groups or substituents are present in R 8 , they can be selected from F and Cl. In embodiments, there are no halide groups or substituents in R 8 .
  • T is either absent, i.e. R 7 and R 8 are directly bonded together, or T is a linking group selected from -O-, -OC(O)- and -C(O)O-, e.g. R 7 -O-R 8 , R 7 -C(O)O-R 8 , or R 7 -OC(O)-R 8 .
  • R 8 is an olefin, a "T" linking group is present.
  • reactive diluents include phenyl glycidyl ether, C 1-30 alkyl phenyl glycidyl ethers (e.g. C 1-12 or C 1-5 alkyl phenyl glycidyl ethers such as methyl phenyl glycidyl ether, ethyl phenyl glycidyl ether, propyl phenyl glycidyl ether and para t-butyl phenyl glycidyl ether), and glycidyl esters of carboxylic acids (e.g. glycidyl esters of fatty acids or versatic acids such as pivalic acid or neodecanoic acid).
  • C 1-30 alkyl phenyl glycidyl ethers e.g. C 1-12 or C 1-5 alkyl phenyl glycidyl ethers such as methyl phenyl glycidyl
  • alkyl glycidyl ethers e.g. C 1-16 alkyl glycidyl ethers, e.g. where m is from 2 to 6.
  • alkyl glycidyl ethers e.g. C 1-16 alkyl glycidyl ethers, e.g. where m is from 2 to 6.
  • examples include glycidyl ethers of di- and polyhydric aliphatic alcohols such as hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidylether, pentaerythritol tetraglycidyl ether, dipentaerythritol polyglycidyl ethers, butanediol diglycidyl ether, neopentylglycol diglycid
  • Still further examples include glycidyl ethers of an aliphatic ether or polyether, e.g. dipropyleneglycol diglycidyl ether.
  • They can also be made by epoxidation of unsaturated fats and oils, for example unsaturated fatty acids, diglycerides or triglycerides having C 4-30 fatty acid or fatty acid ester groups.
  • unsaturated fatty acids for example unsaturated fatty acids, diglycerides or triglycerides having C 4-30 fatty acid or fatty acid ester groups.
  • An example is Cardolite TM NC-513, which is made by reacting epichlorohydrin with an oil obtained from the shells of cashew nuts.
  • the reactive diluent can also be selected from epoxidized olefins, including dienes and polydienes. They can be C 2-30 , C 8-28 , C 6-18 , C 14-16 or C 6-12 epoxidised olefins.
  • They can comprise from 1 to 4 epoxy groups, for example 1 or 2 epoxy groups, such as 2 epoxy groups.
  • Specific examples include diepoxyoctane and epoxidized polybutadiene.
  • Epoxidised polydienes such as polybutadiene can have a molecular weight (number average, M n ) in the range of from 500 to 100000, for example in the range of from 1000 to 50000, or from 2000 to 20000.
  • reactive diluents include dialkyl carbonates, e.g. C 1-16 dialkyl carbonates or C 1-6 dialkyl carbonates, such as dimethyl carbonate.
  • R 7 is a C 4-8 alkyl group.
  • the reactive diluent has from 8 to 14 carbon atoms.
  • the reactive diluent is aliphatic, which can add flexibility to the coating.
  • the reactive diluent is polyfunctional, i.e. m is greater than 1, e.g. from 1 to 8, or from 1 to 6, as this can help to increase drying speeds, and also increase cross-linking density. It can also help contribute to improved anticorrosive properties.
  • More than one reactive diluent can be used, for example combinations of any of those mentioned above.
  • the reactive diluent is present in the first part (A) of a two-component coating composition, i.e. with the curable epoxy binder.
  • the reactive diluent can be present in an amount of from 1.0 to 15.0 wt.%, for example from 2.0 to 12.0 wt%. These amounts can help lower the viscosity of the coating composition, which is advantageous for high solids and low solvent compositions.
  • the viscosity of the reactive diluent is ⁇ 50 cP, for example ⁇ 30 cP, or ⁇ 20 cP at 23°C and 50% RH.
  • the viscosity can be measured using the cone and plate method described in ASTM D4287.
  • a curing agent is used.
  • the curing agent can be selected from polyamides, polyamines, epoxy-amine adducts, phenalkamines, or phenalkamides. Curing agents can also be referred to as crosslinking agents or hardeners.
  • the compound typically contains at least two "reactive" or “active” hydrogen atoms linked to nitrogen on average per molecule.
  • the curing agent typically contains at least two amine groups.
  • the amine groups can be primary or secondary amine groups.
  • Suitable curing agents include amines or amino functional polymers selected from aliphatic (including cycloaliphatic) amines and polyamines, amido amines, polyamido amines, polyoxy alkylene amines (e.g. polyoxyalkylene diamines), aminated polyalkoxy ethers (e.g. those sold commercially as "Jeffamines”), alkylene amines (e.g. alkylene diamines), aromatic amines (including aralkyl amines), Mannich bases (e.g. those sold commercially as "phenalkamines”), amino functional silicones or silanes, and any epoxy adducts and derivatives thereof.
  • aliphatic (including cycloaliphatic) amines and polyamines amido amines, polyamido amines, polyoxy alkylene amines (e.g. polyoxyalkylene diamines), aminated polyalkoxy ethers (e.g. those sold commercially
  • Thiol-based curing agents can also be used, for example compounds comprising 2 or more thiol groups (often termed polythiol or polymercaptan curing agents, as described for example in US5374668 ). Examples include C 1-20 aliphatic or aromatic compounds comprising 2 or more (e.g. 2-4) sulfur atoms in the form of thiol groups.
  • Examples include those listed at column 4, line 53 to column 6, line 63 of US5374668 .
  • One specific example is thiolated norbornene.
  • curing agents are known, for example those listed in WO2018/046702 at page 21, line 10 to page 23, line 10. Other examples include those listed at page 10, line 23 to page 12, line 5 of WO2017/068015 .
  • ethylene diamine, hydroxyethyl ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentaamine, the reaction products with fatty acids or dimer fatty acids, to form amidoamines and amine functional polyamides c.f. " Protective Coatings, Fundamentals of Chemistry and Composition” by Clive H. Hare, publ. Society for Protective Coatings, ISBN 0-938477-90-0 ).
  • Additional examples include dicyandiamide, isophorone diamine, m-xylylene diamine, m-phenylene diamine, 1,3-bis(aminoethyl)cyclohexane, bis(4-aminocyclohexyl) methane, bis(4-amino-3-methycyclohexyl) methane, N-aminoethyl piperazine, 4,4'-diaminediphenyl methane, 4,4'-diamino-3,3'-diethyl diphenyl methane, diaminodiphenyl sulfone, and Mannich base curing agents manufactured using the above polyamine curing agents.
  • Adducts of any of these amines can also be used.
  • Such adducts can be prepared by reaction of the amine with a suitably reactive compound such as a silicon-free epoxy resin or an epoxy functional reactive diluent, for example butyl glycidyl ether.
  • a suitably reactive compound such as a silicon-free epoxy resin or an epoxy functional reactive diluent, for example butyl glycidyl ether.
  • epoxy-functional reactive diluents are described in " Protective Coatings, Fundamentals of Chemistry and Composition", by Clive H. Hare, published by the Society for Protective Coatings (ISBN 0-938477-90-0 ).
  • Adducts of any of these amines can also be prepared by reaction of the amine with a suitably reactive compound such as an acrylate, a maleate, a fumarate, a methacrylate, or even electrophilic vinyl compounds such as acrylonitrile.
  • a suitably reactive compound such as an acrylate, a maleate, a fumarate, a methacrylate, or even electrophilic vinyl compounds such as acrylonitrile.
  • composition can comprise more than one curing agent, e.g. blends of two or more of any of the above curing agents.
  • the curing agent is preferably capable of at least partially curing the epoxy resin at a temperature in the range of -10 to 50°C, for example in the range of from 0 to 40 °C. Mixtures of amine curing agents can also be used.
  • Amine-containing organosilane compounds are not considered curing agents. If they are present in the coating composition, they are used in addition to a curing agent.
  • the curing agent is supplied separately from the binder before use, for example being supplied as a kit containing two parts, the binder part (A), and the curing agent part (B). The two parts are then mixed shortly before application.
  • the viscosity of the curing agent is below 300 cP, for example 100 to 300 cP.
  • Curing agents can optionally be used with a catalyst (or curing accelerator), for example being selected from tertiary amines and phenols. Specific examples include trimethylamine, ethyldimethylamine, propyldimethylamine, N,N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo(5.4.0)undecane-1 (DBU), benzyldimethylamine, 2-(dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris(dimethylaminoethyl) phenol (DMP-30), phenol novolac, o-cresol novolac, p-cresol novolac, t-butylphenol novolac, and dicyclopentadiene cresol.
  • a catalyst or curing accelerator
  • catalysts include p-toluenesulfonic acid and amino-aliphatic heterocyclic salts of thiocyanic acids, e.g. the 1-aminopyrrolidone salt of thiocyanic acid (as described, for example, in US6503967 .
  • the amount of curing agent in the total coating composition is in the range of from 10 to 35.0 wt%, for example from 10.0 to 30.0 wt.%, or for from 12.0 to 25.0 wt.%.
  • AHE Active hydrogen equivalents
  • AHEW active hydrogen equivalent weight
  • EE epoxy equivalents
  • EW epoxy equivalent weight
  • the epoxy equivalent weight (EEW) of an epoxy-containing compound is the weight of the compound that yields one mole (or one equivalent) of epoxy functional groups.
  • the active hydrogen equivalent weight (AHEW) of a compound is the weight of the curing agent required to yield one mole (or one equivalent) of active hydrogens (i.e. those present in an -NH- or -NH 2 group).
  • the calculation is based on the curing agent before adduct formation.
  • the molar ratio of epoxy groups to active hydrogens is in the range of from 0.6 to 2.0, for example from 0.8 to 1.7.
  • the polyphosphate to be used is selected from alkaline earth metal aluminium polyphosphates, including their silicates and their hydrates.
  • the alkaline earth metal is typically selected from magnesium, calcium and strontium, for example from calcium and strontium.
  • examples of polyphosphates include magnesium aluminium polyphosphate, calcium aluminium polyphosphate silicate, strontium aluminium polyphosphate, and hydrates thereof. Combinations of these can be used.
  • the polyphosphate is selected from calcium aluminium polyphosphate silicate hydrate and strontium aluminium polyphosphate hydrate.
  • the amount of polyphosphate in the coating composition is in the range of from 0.05 to 10.0 wt%, for example from 0.1 to 10.0 wt%, from 1.0 to 10.0 wt.%, of from 2.0 to 6.0 wt%.
  • Polyphosphates can be defined in terms of a degree of polymerisation, i.e. how many phosphate groups are included in the polyphosphate anion.
  • the degree of polymerisation is in the range of from 2 to 10, for example from 2 to 7, from 3 to 10, from 3 to 7 or from 3 to 5. In embodiments, the degree of polymerisation is 3.
  • the polyphosphate ion can be represented by the following formula: j is at least 2, for example in the range of from 2 to 10 or from 2 to 7. In embodiments, j is 3 or more, for example from 3 to 10, from 3 to 7 or from 3 to 5. In further embodiments, j is 3.
  • (j+2)- is the formal negative charge on the polyphosphate ion.
  • the negative charge is balanced by positive charges from cations, which formally have +3 and +2 charges.
  • the +3 cation is aluminium
  • the +2 cation(s) is (are) selected from alkaline earth ions.
  • the polyphosphate can be included in either part (A) or part (B) of a 2-component composition.
  • the coating composition may also contain other components, for example one or more auxiliary anti corrosion additives, pigments, fillers and extenders, thixotropic agents, plasticizers, inorganic and organic dehydrators (stabilizers), UV stabilizers, antifouling agents, defoamers or combinations thereof.
  • auxiliary anti corrosion additives for example one or more auxiliary anti corrosion additives, pigments, fillers and extenders, thixotropic agents, plasticizers, inorganic and organic dehydrators (stabilizers), UV stabilizers, antifouling agents, defoamers or combinations thereof.
  • the total amount of such further optional components can be in the range of from 0 to 65 wt%.
  • Fillers and extenders include those with a low oil absorption value, such as barium sulfate (including baryte), glass spheres, feldspar, calcite, silica, aluminum oxide, zirconium oxide, dolomite, kaolin or wollastonite and optionally a laminar type of extender such as mica, talc, aluminum flakes, chlorite and china clay.
  • a low oil absorption value such as barium sulfate (including baryte), glass spheres, feldspar, calcite, silica, aluminum oxide, zirconium oxide, dolomite, kaolin or wollastonite and optionally a laminar type of extender such as mica, talc, aluminum flakes, chlorite and china clay.
  • One or more fillers can be used.
  • the amount of filler in the coating composition can be in the range of from 20.0 to 50.0 wt%.
  • inorganic auxiliary corrosion inhibitors examples include silicates (such as potassium silicate and aluminium silicate), hydrogen phosphates (such as calcium hydrogen phosphate, magnesium hydrogen phosphate, and strontium hydrogen phosphate), phosphates (such as zinc phosphate, zinc orthophosphate, zinc orthophosphate hydrate, zinc aluminium orthophosphate, and organically modified basic zinc orthophosphate), phosphosilicates (such as calcium strontium phosphosilicate and strontium zinc phosphosilicate), borophosphates (such as strontium borophosphate), molybdates, tungstates, vanadates, and metals (such as zinc dust, zinc powder, zinc alloy, magnesium, and magnesium alloy).
  • silicates such as potassium silicate and aluminium silicate
  • hydrogen phosphates such as calcium hydrogen phosphate, magnesium hydrogen phosphate, and strontium hydrogen phosphate
  • phosphates such as zinc phosphate, zinc orthophosphate, zinc orthophosphate hydrate, zinc aluminium orthophosphate, and
  • organic auxiliary corrosion inhibitors include azoles, such as imidazoles, thiazoles, tetrazoles, and triazoles, e.g. (substituted) benzotriazole, and 2-mercaptobenzothiazole; amines, such as N-phenyl-1.4-phenylenediamine and Schiff bases such as N,N' o-phenylen-bis(3-methoxysalicylidenimine); amino acids, such as tryptophan thiole group-containing compounds such as DMTD (2-5,dimercapto-1,3,4-thiadiazole) and 1-phenyl-2,5-dithiohydrazodicarbonamide; phthalazine derivatives, such as 2-[(7-anilino-5-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-3-yl)methyl]phthalazine-1(2H)-one; tannins and substituted uracils; phosphoric
  • More than one auxiliary corrosion inhibitor can be used. They can be present in total in the composition in an amount ranging from 1 to 20 % solids volume.
  • the coating composition may be prepared by any suitable technique.
  • the constituents are mechanically mixed, for example using a high-speed disperser, a ball mill, a pearl mill, a three-roll mill or an inline mixer.
  • compositions may be filtered, for example using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM tumoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration.
  • the epoxy resin-containing component (part A) and the curing agent component (part B) can be mixed and stirred until homogeneous. The mixture can then be applied to a substrate, optionally after a prior induction time.
  • the coating composition can be applied to a substrate (for example a steel structure) by known methods, for example by conventional air-spraying, by airless- or airmix-spraying equipment, or by 2K airless spray pumps. It can alternatively be applied using brush or roller, for example when used as a stripe coat.
  • the composition can be applied at ambient conditions without pre-heating the coating composition. In spraying applications, conventional pressures such as 3 to 5 bars can be used.
  • the coating is typically applied so that a total dry film thickness of from 100-1000 ⁇ m is obtained, such as 100 to 500 ⁇ m or 150-350 ⁇ m.
  • the applied film thickness can vary depending on the nature of substrate being coated and the environment to which it will be exposed.
  • the coating composition can be used on its own, e.g. where is used as a ballast tank coating.
  • it can form part of a coating system comprising more than one coating composition.
  • it can be a primer, a self-priming top-coat, an intermediate coat or a top coat. It can be applied to pre-treated or non pre-treated substrates.
  • the coating composition as described above is an anticorrosive primer coating composition. It can be used in a coating system in combination with one or more top coats, which can be selected from cleartop coats and pigmented top coats. In further embodiments, the coating composition can be used as a universal primer, i.e. that prepares a surface for subsequent coating.
  • Part A and Part B Each part of a 2-part composition (Part A and Part B) was separately blended using a high-speed dispersion apparatus in the amounts specified in Table 1. Comparative examples are indicated by an asterisk (*).
  • the Part A and Part B compositions were then mixed together prior to being applied to a substrate.
  • Test coatings were applied by airless spray onto pre-treated steel panels so as to obtain a dry film thickness of 160 ⁇ m.
  • the steel surfaces were pre-treated by grit-blasting to Sa 2.5, according to ISO 8501-1, with an average surface roughness profile between 55 and 95 ⁇ m, according to ISO 8503-2.
  • the coatings were allowed to cure at 23 ⁇ 2 °C at 50% relative humidity (RH) for 7 days before testing.
  • Table 1 - Coating compositions (amounts in weight parts) Component Ex. 1* Ex. 2 Ex. 3 Ex. 4* Ex. 5* Ex. 6* Ex.
  • Pull-off adhesion test The minimum tensile stress needed to detach or rupture a coating was tested. The test was carried out in accordance with ISO 4624:2016, by first securing loading fixtures (dollies) perpendicular to the surface of a coating with an adhesive. The testing apparatus was then attached to the loading fixture and aligned to apply tension perpendicular to the test surface. The applied force (MPa) was gradually increased and monitored until either a plug of the coating detached, or a previously specified value was reached.
  • Pen-knife adhesion test This test (“knife-adhesion test”) was carried out in accordance with ASTM D6677. In this test, an "X" was cut in the surface of the coating, and the knife-blade was used to gently lift the cut portion of the coating from the substrate. The extent of adhesion of the coating to the substrate was determined by seeing how clean the surface was after the coating was lifted. A clear surface meant that adhesion to the steel substrate was poor. A surface still comprising portions of coating meant that adhesion to the surface was improved, the lifted material having detached through failure of coating cohesion, not through failure of coating/substrate adhesion.
  • the extent of coating remaining on the surface was qualitatively measured on a scale of 0 to 10, with 0 indicating no residual surface coating (i.e. complete failure of adhesion) and 10 indicating no uncovered substrate surface (i.e. complete failure of coating cohesion, and no failure of coating adhesion).
  • EIS Electrochemical Impedance Spectroscopy
  • Examples 1 to 3 were immersed in fresh water or seawater at 40 °C for 18 months. After the 18 month immersion period, the samples were analysed by EIS, and the results are shown in Table 2. Table 2 - Impedance after 40 °C immersion for 18 months Example Fresh water ( ⁇ cm 2 ) Sea water ( ⁇ cm 2 ) 1* 2.20 ⁇ 10 7 1.17 ⁇ 10 9 2 8.05 ⁇ 10 9 2.36 ⁇ 10 9 3 2.92 ⁇ 10 9 2.33 ⁇ 10 9
  • compositions were also tested for adhesion to the steel substrate by the knife-adhesion test. Results are shown in Table 3. Table 3 - Knife adhesion tests after 40 °C immersion for 18 months Example Fresh water Sea water 1* 4 6 2 10 10 3 10 10
  • Examples 1-2 and 4-7 were immersed in fresh water or sea water at 50 °C for 3 months. After the immersion period, EIS measurement were collected, and knife adhesion and pull-off tests were performed, with results shown in Tables 4, 5 and 6 respectively.
  • Examples 1-2 and 4-7 were immersed in sea water at 40 °C for 15 months. After the immersion period, EIS measurements were collected and pull-off tests were performed, with results shown in Table 7. The inventive example performs better than the comparative examples in both tests, supporting the observations from Experiments 1 and 2.
  • Table 7 - EIS measurements and pull-off adhesion tests after 40 °C sea water immersion for 15 months Example Sea Water ( ⁇ cm 2 ) Sea Water (MPa) 1* 7.35 ⁇ 10 9 5.16 2 1.46 ⁇ 10 10 8.99 4* 1.14 ⁇ 10 10 4.24 5* 1.24 ⁇ 10 10 3.92 6* 3.79 ⁇ 10 9 4.43 7* 1.01 ⁇ 10 10 4.00

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (15)

  1. Composition de revêtement comprenant
    - 10,0 à 40,0 % en poids d'une résine époxy durcissable,
    - 10,0 à 35,0 % en poids d'un agent de durcissement,
    - 0,05 à 10,0 % en poids d'un ou plusieurs composés choisis parmi des polyphosphates d'aluminium alcalino-terreux et leurs silicates et hydrates ;
    la composition ayant une teneur en solides d'au moins 90 % en poids et/ou un volume de solides d'au moins 90,0 %, lorsqu'ils sont déterminés selon la norme ASTM D5201.
  2. Composition de revêtement selon la revendication 1, le métal alcalino-terreux du polyphosphate d'aluminium alcalino-terreux étant choisi parmi le calcium et le strontium.
  3. Composition de revêtement selon la revendication 2, le polyphosphate d'aluminium alcalino-terreux étant choisi parmi le polyphosphate d'aluminium de strontium et l'hydrate de silicate de polyphosphate d'aluminium de calcium.
  4. Composition de revêtement selon l'une quelconque des revendications 1 à 3, la résine époxy durcissable comprenant deux groupes aromatiques ou hétéroaromatiques.
  5. Composition de revêtement selon la revendication 4, dans laquelle la résine époxy durcissable comprend deux groupes époxy ou groupes époxy éther ou plus.
  6. Composition de revêtement selon la revendication 4 ou la revendication 5, dans laquelle
    (a) la résine époxy durcissable est choisie parmi des résines d'éther de diglycidyle de bisphénol A, des résines d'éther de diglycidyle de bisphénol F, des résines d'éther de diglycidyle de bisphénol S, des résines d'éther de diglycidyle de résorcinol et des résines d'éther de glycidyle de novolaque ; et/ou ;
    (b) l'agent de durcissement étant choisi parmi des polyamides, des polyamines, des adduits époxy-amine, des phénalcamines, des phénalcamides et des polythiols.
  7. Composition de revêtement selon l'une quelconque des revendications 1 à 6, la composition de revêtement étant une composition d'apprêt.
  8. Composition de revêtement selon l'une quelconque des revendications 1 à 7, l'un ou plusieurs des énoncés suivants s'appliquant :
    (a) la composition comprend de 1 à 15 % en poids d'un silane organique ;
    (b) la composition comprend de 1 à 15 % en poids d'un diluant réactif ;
    (c) la composition de revêtement comprend 20 à 50 % en poids de charge ;
    (d) la composition comprend de 10,0 à 25,0 % en poids d'agent de durcissement
    (e) la composition comprend de 2,0 à 6,0 % en poids de polyphosphate d'aluminium alcalino-terreux ;
    (f) la composition de revêtement comprend 1 % en poids ou moins d'eau ;
    (g) la résine époxy durcissable possède un poids moléculaire moyen en nombre dans la plage allant de 100 à 2 000 ;
    (h) la teneur en solvant et/ou en VOC de la composition de revêtement est inférieure à 5 % en poids ;
    (i) le rapport d'équivalents d'époxy sur les hydrogènes actifs dans la composition de revêtement est dans la plage allant de 0,6 à 2,0.
  9. Composition de revêtement selon la revendication 8, dans laquelle un ou plusieurs des énoncés suivants s'appliquent :
    (a) le silane organique comprend un groupe époxy ;
    (b) le diluant réactif est choisi parmi des résines contenant époxy qui sont aliphatiques, ou qui comprennent pas plus d'un groupe aromatique ou hétéroaromatique ;
    (c) le diluant réactif est choisi parmi l'éther de phényle et de glycidyle, les éthers de glycidyle et d'alkylphényle, les esters de glycidyle d'acides carboxyliques, les éthers d'alkyle et de glycidyle, les graisses et huiles insaturées époxydées, les oléfines époxydées, les diènes époxydés et les polydiènes époxydés.
  10. Substrat revêtu par une composition de revêtement selon l'une quelconque des revendications 1 à 9 séchée ou durcie.
  11. Procédé pour la protection d'un substrat par application sur sa surface d'une composition de revêtement selon l'une quelconque des revendications 1 à 10.
  12. Procédé selon la revendication 11, dans lequel :
    (a) le substrat est métallique ; et/ou
    (b) le substrat est immergé sous la surface de l'eau de mer ou de l'eau douce pendant des périodes de temps étendues, par exemple une coque de bateau, un ballast de bateau ou une partie submergée d'une structure ou d'une plate-forme mobile ou fixe.
  13. Procédé selon l'une quelconque des revendications 11 à 12, dans lequel le revêtement est appliqué par pulvérisation.
  14. Procédé selon l'une quelconque des revendications 11 à 13, dans lequel une composition de revêtement différente supplémentaire est appliquée subséquemment au-dessus de la composition de revêtement selon l'une quelconque des revendications 1 à 9.
  15. Procédé selon l'une quelconque des revendications 11 à 14, dans lequel la composition de revêtement et/ou la composition de revêtement différente supplémentaire est/sont laissée(s) à sécher ou durcir, éventuellement après l'application de chaleur.
EP20816206.5A 2019-12-05 2020-12-03 Composition de revêtement à faible teneur en solvant Active EP4069789B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19213944 2019-12-05
EP19217045 2019-12-17
PCT/EP2020/084451 WO2021110829A1 (fr) 2019-12-05 2020-12-03 Composition de revêtement à faible teneur en solvant

Publications (2)

Publication Number Publication Date
EP4069789A1 EP4069789A1 (fr) 2022-10-12
EP4069789B1 true EP4069789B1 (fr) 2024-05-22

Family

ID=73642904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20816206.5A Active EP4069789B1 (fr) 2019-12-05 2020-12-03 Composition de revêtement à faible teneur en solvant

Country Status (7)

Country Link
EP (1) EP4069789B1 (fr)
JP (1) JP7377357B2 (fr)
CN (1) CN114761499A (fr)
AU (1) AU2020397212A1 (fr)
BR (1) BR112022009758A2 (fr)
CA (1) CA3162882A1 (fr)
WO (1) WO2021110829A1 (fr)

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61110545A (ja) * 1984-11-02 1986-05-28 川崎製鉄株式会社 防錆塗装鋼材
US4927749A (en) 1986-04-09 1990-05-22 Jeanette Simpson Reagent for cell separation
CN1040810A (zh) 1988-04-30 1990-03-28 三井东圧化学株式会社 多硫化合物基树脂透镜及其制备方法
WO2001029109A1 (fr) 1999-10-19 2001-04-26 Otsuka Kagaku Kabushiki Kaisha Agent de durcissement pour resine epoxy et composition de resine epoxy
DE102008006391B4 (de) * 2008-01-28 2016-11-17 Airbus Operations Gmbh Chromatfreie Zusammensetzung, deren Verwendung als Korrosionsschutz und damit hergestellte Korrosionsschutzbeschichtung für Kraftstofftanks
ES2524433T3 (es) 2009-04-03 2014-12-09 Akzo Nobel Coatings International B.V. Revestimiento en polvo resistente a la corrosión y al desconchado
US8628689B2 (en) 2009-04-03 2014-01-14 Akzo Nobel Coatings International B.V. Anti-corrosive coating composition
US8871888B2 (en) 2009-05-22 2014-10-28 Ppg Industries Ohio, Inc One-component epoxy coating compositions
US20120094130A1 (en) * 2010-10-15 2012-04-19 Universidade Estadual De Campinas Coating Compositions With Anticorrosion Properties
CN102993913B (zh) 2012-12-19 2015-09-23 上海海隆赛能新材料有限公司 一种用于定向钻穿管道的无溶剂防腐涂料及其制备方法
CN103087612B (zh) * 2013-01-30 2016-01-20 株洲飞鹿高新材料技术股份有限公司 室温快干高防腐双组分水性环氧涂料及其制备方法
JP6453775B2 (ja) 2013-03-08 2019-01-16 スリーエム イノベイティブ プロパティズ カンパニー ゲル封止防食テープ
KR20150051106A (ko) 2013-10-30 2015-05-11 아크조노벨코팅스인터내셔널비.브이. 분말 코팅 조성물
JP6661008B2 (ja) 2015-10-23 2020-03-11 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ 化学設備における表面用コーティング方法
RU2755901C2 (ru) 2016-09-08 2021-09-22 Йотун А/С Покрытия
CN106800861B (zh) 2016-12-27 2019-04-19 天津灯塔涂料工业发展有限公司 一种无铬高固体双组分环氧底漆及其制备方法
US11434380B2 (en) * 2017-03-24 2022-09-06 3M Innovative Properties Company Aqueous primer composition and related methods
CN109401553A (zh) 2018-11-12 2019-03-01 中国航发北京航空材料研究院 一种镉、锌镀层表面用无溶剂防腐涂料极其制备方法

Also Published As

Publication number Publication date
CN114761499A (zh) 2022-07-15
KR20220102643A (ko) 2022-07-20
EP4069789A1 (fr) 2022-10-12
CA3162882A1 (fr) 2021-06-10
JP2023504392A (ja) 2023-02-03
WO2021110829A1 (fr) 2021-06-10
AU2020397212A1 (en) 2022-06-02
BR112022009758A2 (pt) 2022-08-16
JP7377357B2 (ja) 2023-11-09

Similar Documents

Publication Publication Date Title
CN102732130B (zh) 一种适合喷涂的高固体分防腐蚀涂料及其制备方法
CN104619741B (zh) 液体环氧树脂涂料组合物、方法和制品
WO2014136752A1 (fr) Composition de peinture anticorrosion, revêtement anticorrosion et procédé destiné à empêcher la corrosion d'un matériau de base
WO2007046301A1 (fr) Composition de revêtement en résine époxyde polyfonctionnelle contenant un pigment antirouille, film de revêtement obtenu à partir de celle-ci, base recouverte du film de revêtement et procédé de protection contre la rouille
KR20160007493A (ko) 에폭시 수지 조성물
WO2009076609A2 (fr) Revêtements à base de carbamate de glycidyle ayant une meilleure résistance à la corrosion
CN110914329B (zh) 组合物
EP2528979A1 (fr) Compositions d'apprêt à base d'époxyde
WO2017140610A1 (fr) Procédé de revêtement d'une cale de chargement
EP4069789B1 (fr) Composition de revêtement à faible teneur en solvant
US20070123664A1 (en) Multi-component epoxy-amine compositions
KR102684176B1 (ko) 저용매 코팅 조성물
EP4202002A1 (fr) Composition de revêtement exempte de solvant
US20230088913A1 (en) Amine-epoxy resin addition product
US20230103342A1 (en) Curing agents for epoxy resin coatings
EP2239293A1 (fr) Agents durcisseurs pour revêtements époxy
US20210301077A1 (en) Accelerator for curing epoxy resins comprising alkylated amines
US20210246257A1 (en) Hardener for epoxy resins
WO2007034713A1 (fr) Composition de resine epoxy
JP7429795B2 (ja) 低ｖｏｃ塗料組成物、塗膜および塗膜付き基材ならびにこれらの製造方法
EP3864094B1 (fr) Peintures époxy à deux composants présentant une meilleure protection contre la corrosion
AU2021245972B2 (en) Aqueous coating composition containing an epoxy-amine system and an aromatic carboxylic acid as curing catalyst
US20230331903A1 (en) Adduct of alkylated diamine and novolak epoxy resin
WO2023194444A1 (fr) Revêtements
US20230068858A1 (en) Amine epoxy resin adduct

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220331

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230720

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MIN, SEONGWOON

Inventor name: KIM, MIHYANG

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20240103

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20240501

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020031376

Country of ref document: DE